JPS63225301A - Production of agricultural chemical pharmaceutical - Google Patents
Production of agricultural chemical pharmaceuticalInfo
- Publication number
- JPS63225301A JPS63225301A JP5760387A JP5760387A JPS63225301A JP S63225301 A JPS63225301 A JP S63225301A JP 5760387 A JP5760387 A JP 5760387A JP 5760387 A JP5760387 A JP 5760387A JP S63225301 A JPS63225301 A JP S63225301A
- Authority
- JP
- Japan
- Prior art keywords
- gel
- agricultural chemical
- agricultural
- pharmaceutical
- ingredients
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003905 agrochemical Substances 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- -1 alkyl silicate Chemical compound 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000004009 herbicide Substances 0.000 claims abstract description 13
- 230000002363 herbicidal effect Effects 0.000 claims abstract description 12
- 230000007062 hydrolysis Effects 0.000 claims abstract description 12
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000000575 pesticide Substances 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 8
- 238000009472 formulation Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 21
- 239000004615 ingredient Substances 0.000 abstract description 12
- 239000000843 powder Substances 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 5
- 239000002917 insecticide Substances 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 230000002459 sustained effect Effects 0.000 abstract description 2
- 231100000674 Phytotoxicity Toxicity 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 235000001602 Digitaria X umfolozi Nutrition 0.000 description 7
- 240000003176 Digitaria ciliaris Species 0.000 description 7
- 235000017898 Digitaria ciliaris Nutrition 0.000 description 7
- 235000005476 Digitaria cruciata Nutrition 0.000 description 7
- 235000006830 Digitaria didactyla Nutrition 0.000 description 7
- 235000005804 Digitaria eriantha ssp. eriantha Nutrition 0.000 description 7
- 235000010823 Digitaria sanguinalis Nutrition 0.000 description 7
- 235000014716 Eleusine indica Nutrition 0.000 description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 6
- 230000035784 germination Effects 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 238000001879 gelation Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002689 soil Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 240000008042 Zea mays Species 0.000 description 3
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 3
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 235000005822 corn Nutrition 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000012456 homogeneous solution Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- XMTQQYYKAHVGBJ-UHFFFAOYSA-N 3-(3,4-DICHLOROPHENYL)-1,1-DIMETHYLUREA Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C(Cl)=C1 XMTQQYYKAHVGBJ-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 230000005923 long-lasting effect Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000013268 sustained release Methods 0.000 description 2
- 239000012730 sustained-release form Substances 0.000 description 2
- 239000005631 2,4-Dichlorophenoxyacetic acid Substances 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 239000005484 Bifenox Substances 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000005510 Diuron Substances 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- SUSRORUBZHMPCO-UHFFFAOYSA-N MC-4379 Chemical compound C1=C([N+]([O-])=O)C(C(=O)OC)=CC(OC=2C(=CC(Cl)=CC=2)Cl)=C1 SUSRORUBZHMPCO-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- OCBFFGCSTGGPSQ-UHFFFAOYSA-N [CH2]CC Chemical compound [CH2]CC OCBFFGCSTGGPSQ-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- MXWJVTOOROXGIU-UHFFFAOYSA-N atrazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)C)=N1 MXWJVTOOROXGIU-UHFFFAOYSA-N 0.000 description 1
- VEMKTZHHVJILDY-UXHICEINSA-N bioresmethrin Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OCC1=COC(CC=2C=CC=CC=2)=C1 VEMKTZHHVJILDY-UXHICEINSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- HKPHPIREJKHECO-UHFFFAOYSA-N butachlor Chemical compound CCCCOCN(C(=O)CCl)C1=C(CC)C=CC=C1CC HKPHPIREJKHECO-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000000679 carrageenan Substances 0.000 description 1
- 235000010418 carrageenan Nutrition 0.000 description 1
- 229920001525 carrageenan Polymers 0.000 description 1
- 229940113118 carrageenan Drugs 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- BIWJNBZANLAXMG-YQELWRJZSA-N chloordaan Chemical compound ClC1=C(Cl)[C@@]2(Cl)C3CC(Cl)C(Cl)C3[C@]1(Cl)C2(Cl)Cl BIWJNBZANLAXMG-YQELWRJZSA-N 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000007952 growth promoter Substances 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 229940071826 hydroxyethyl cellulose Drugs 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 229940071676 hydroxypropylcellulose Drugs 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- LZGUHMNOBNWABZ-UHFFFAOYSA-N n-nitro-n-phenylnitramide Chemical class [O-][N+](=O)N([N+]([O-])=O)C1=CC=CC=C1 LZGUHMNOBNWABZ-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 239000003090 pesticide formulation Substances 0.000 description 1
- LCPDWSOZIOUXRV-UHFFFAOYSA-N phenoxyacetic acid Chemical class OC(=O)COC1=CC=CC=C1 LCPDWSOZIOUXRV-UHFFFAOYSA-N 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 229940075065 polyvinyl acetate Drugs 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000003128 rodenticide Substances 0.000 description 1
- 235000015170 shellfish Nutrition 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- ODCWYMIRDDJXKW-UHFFFAOYSA-N simazine Chemical compound CCNC1=NC(Cl)=NC(NCC)=N1 ODCWYMIRDDJXKW-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、農薬の薬効成分を担持した農薬製剤の製造方
法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing an agrochemical formulation carrying a medicinal ingredient of an agrochemical.
農薬は土壌や植物等に施されるが、施した農薬が安定で
かつ効果の持続性に優れるものが好ましい。しかしなが
ら、現実には効果の持続性を達成することがむずかしく
、一度に必要以上の農薬を散布するか又は散布回数を増
やして対応しているのが現状である。ところが、多量に
散布する場合には対象物以外への影響、たとえば薬害や
残留などの問題が大きい上に、非常に不経済であり、一
方散布団数を増す場合には散布の手間がかかり、省力化
が望まれている現状を考えると好ましくない。さらに、
これらの方法によると農薬が雨により流出して河川に侵
入し魚貝類に被害がでたり、又除草剤の場合には、雨で
農薬が土中深くまで拡散し、作物の根に達し、作物への
薬害がでる等の問題がある。Pesticides are applied to soil, plants, etc., and it is preferable that the applied pesticide is stable and has excellent long-lasting effects. However, in reality, it is difficult to achieve a sustained effect, and the current situation is to spray more pesticides than necessary at one time or to increase the number of sprays. However, when spraying in large quantities, there are serious problems with the effects on objects other than the target, such as chemical damage and residue, and it is also extremely uneconomical.On the other hand, when the number of spraying groups is increased, spraying takes time and effort. Considering the current situation where labor saving is desired, this is not desirable. moreover,
According to these methods, pesticides run off in the rain and enter rivers, causing damage to fish and shellfish.In addition, in the case of herbicides, the pesticides spread deep into the soil due to rain, reaching the roots of crops, and damaging the crops. There are problems such as chemical damage to the skin.
これに対して、農薬自体が安定で寿命の長いものを用い
ることが考えられるが、このような農薬は逆に分解も遅
く、長期間残留し、食物連鎖にとり込まれる可能性があ
り、近年その使用が著しく制限されている。One way to deal with this is to use pesticides that are stable and long-lived, but on the other hand, such pesticides decompose slowly, remain for a long time, and may be incorporated into the food chain. Use is severely restricted.
そこで寿命が短く残効性の低い農薬の効力を種々の手段
により長期間持続させる方法が開発されている。例えば
、高分子によるマイクロカプセルを用いて農薬をマイク
ロカプセル化する方法があるが、この方法は、高分子の
生分解性が悪く、環境に悪影響をおよぼしやすいという
問題があり、又、タルク、クレー、シリカなどの無機物
に農薬を吸着させるという方法があるが、この方法では
耐水性がなく、雨等や多量の水で農薬が一度に放出され
てしまうという問題がある。Therefore, various methods have been developed to maintain the efficacy of pesticides with short lifespans and low residual effects over long periods of time. For example, there is a method of microencapsulating pesticides using polymeric microcapsules, but this method has the problem that the polymer has poor biodegradability and is likely to have a negative impact on the environment. There is a method in which pesticides are adsorbed onto inorganic substances such as silica, but this method is not water resistant and has the problem that the pesticides are released all at once by rain or large amounts of water.
さらに、農薬用担体として細孔径分布のうち150Å以
下の細孔が占める容積が0.5〜2CC/gである粉状
水和ケイ酸を用いこれに農薬を混合して用いる方法(特
開昭55−85502号)、該担体として、特定の2種
類の細孔半径を有するものが特定の割合にあるものを用
いる方法(特開昭56−86102号)及び水に対する
浸漬熱が1Qcaβ/g以下である微粉水和ケイ酸を用
いる方法(特開昭59−148702号)などが提案さ
れている。しかしながら、これらの方法では担体を調製
した後、これに農薬成分を添加して担体に吸着させてお
り、農薬の持続性については未だ不十分であった。Furthermore, a method of using powdered hydrated silicic acid in which the volume occupied by pores of 150 Å or less in the pore size distribution is 0.5 to 2 CC/g as a carrier for agricultural chemicals, and mixing the agricultural chemicals with this 55-85502), a method using a carrier having a specific ratio of two specific types of pore radii (Japanese Patent Application Laid-open No. 56-86102), and a method in which the heat of immersion in water is 1Qcaβ/g or less A method using finely powdered hydrated silicic acid (Japanese Unexamined Patent Publication No. 148702/1983) has been proposed. However, in these methods, after preparing a carrier, pesticide components are added to the carrier and adsorbed onto the carrier, and the sustainability of the pesticide is still insufficient.
従って、本発明は、土壌や植物等に施したときに農薬の
持続性が高く、耐水性があり、かつ薬害を生じない農薬
製剤の製造方法を提供することを目的とする。Therefore, an object of the present invention is to provide a method for producing an agrochemical formulation that has high persistence, water resistance, and does not cause chemical damage when applied to soil, plants, etc.
本発明は、特定のアルキルシリケートを加水分解、重縮
合反応させてゲルを形成させる際に少くとも1種の農薬
成分を存在させるか又はゲル形成後に農薬成分を添加し
てゲルに含浸させた後に、ゲルを乾燥すると、農薬成分
が粉体の内部にまで十分含まれた形態のものが得られ、
これによれば農薬成分が粉体内部から徐放されるので上
記問題点が極めて有効に解決できるとの知見に基づいて
なされたのである。The present invention is characterized in that at least one pesticide component is present when a specific alkyl silicate is subjected to hydrolysis and polycondensation reaction to form a gel, or after the gel is formed, the pesticide component is added and impregnated into the gel. When the gel is dried, a form in which the pesticide ingredients are sufficiently contained inside the powder is obtained.
This was done based on the knowledge that the above-mentioned problems could be solved very effectively since the agricultural chemical components would be released slowly from inside the powder.
すなわち、本発明は、
一般式〔■〕 :
(式中、R1−R4は、水素又は
CXH2X−+ (OCJ4)y(但し、Xは1〜5、
yは0〜10の整数を示す。)で示される基であるが、
R1−R4のすべてが水素であることはない。nは0〜
20の整数である。)で表わされる少なくとも1種のア
ルキルシリケートの加水分解、重縮合反応を農薬成分の
存在で行ってゲルを形成させた後、又は該反応によりゲ
ルを形成した後に農薬成分を該ゲルに含浸させた後、乾
燥することを特徴とする農薬製剤の製造方法を提供する
。That is, the present invention is based on the general formula [■]: (wherein, R1-R4 are hydrogen or CXH2X-+ (OCJ4)y (wherein, X is 1 to 5,
y represents an integer of 0 to 10. ) is a group represented by
Not all of R1-R4 are hydrogen. n is 0~
It is an integer of 20. ) A hydrolysis or polycondensation reaction of at least one alkyl silicate represented by () is performed in the presence of a pesticide component to form a gel, or after a gel is formed by the reaction, the gel is impregnated with a pesticide component. Provided is a method for producing an agrochemical formulation, which is characterized in that the agrochemical formulation is then dried.
本発明では、上記一般式CI〕で表わさるアルキルシリ
ケートを原料として用いる。このうち、式中、R1−R
4としてはCH3、C2H8、n−C3H7,”l
150−C3Ht 、n−C4tls 、−C2HJ
CLが好ましく、特に好ましくはR1−R4が同一の基
である。又、Xとしては1〜3が、yとしては0〜2が
好ましく、nは0〜10が好ましい。このうち、本発明
ではn=oのものが特に好ましいが、nが1〜10の縮
合体も好ましい。一般式〔I〕で表わされるケイ酸エス
テルを具体的に示すと、ケイ酸メチル、ケイ酸エチル、
ケイ酸n−プロピル、ケイ酸イソプロピノペケイ酸n−
プチノペケイ酸2−メトキシエチノペこれらの2〜10
量体等があげられる。これらのうち、ケイ酸エチルSt
(OC2H5) sはエチルシリケート28、ケイ酸
エチルの平均5モル縮合物:
は、エチルシリケート40としてコルコート社より容易
に入手し得る。In the present invention, an alkyl silicate represented by the above general formula CI] is used as a raw material. Among these, in the formula, R1-R
4 is CH3, C2H8, n-C3H7,"l
150-C3Ht, n-C4tls, -C2HJ
CL is preferred, particularly preferably R1-R4 are the same group. Further, X is preferably 1 to 3, y is preferably 0 to 2, and n is preferably 0 to 10. Among these, in the present invention, those where n=o are particularly preferred, but condensates where n is 1 to 10 are also preferred. Specific examples of the silicate ester represented by the general formula [I] include methyl silicate, ethyl silicate,
n-propyl silicate, isopropinope silicate n-
Putinopesiliic acid 2-methoxyethinope These 2 to 10
Examples include quantities. Among these, ethyl silicate St
(OC2H5) s is ethyl silicate 28, an average 5 mol condensate of ethyl silicate: is easily available as ethyl silicate 40 from Colcourt.
上記ケイ酸エステル又はその縮合物は、水又は水/アル
コール溶媒、酸又はアルカリ触媒下で加水分解し、この
均一溶液を放置、又はpHl製後に放置してゲル化させ
る。この際強いゲルを得るには酸触媒下で加水分解する
のがよい。尚、上記反応において、加水分解と同時にケ
イ酸エステル間に重縮合反応が生じ、5i−0−3i結
合が3次元で生じ安定なゲルが生成する。The above-mentioned silicate ester or condensate thereof is hydrolyzed in water or a water/alcohol solvent, or under an acid or alkali catalyst, and the homogeneous solution is allowed to stand, or left to gel after being made into a pH l. At this time, in order to obtain a strong gel, it is preferable to perform hydrolysis under an acid catalyst. In the above reaction, a polycondensation reaction occurs between the silicate esters simultaneously with the hydrolysis, and 5i-0-3i bonds are formed in three dimensions to form a stable gel.
本発明では上記ゲルを形成させるための加水分解、重縮
合反応を農薬成分の存在下に行わせるか、又はゲル形成
後に農薬成分をゲルに含浸させることを特徴とする。こ
こで使用できる農薬成分としては、農薬に配合される成
分であって、水又はアルコールに可溶若しくは界面活性
剤により乳化又は分散可能なものであればいかなる成分
であってもよい。尚、農薬で水和剤、乳剤、液剤、水溶
剤等製剤化されているものをも使用可能である。具体的
には、トリアジン系(シマジン、アトラジンなど)、ジ
ニトロアニリン系(トリフルアリンなど)、フェノキシ
酢酸系(2,4−D、2.4−PAなど)、アミド系(
ブタクロールなど)、ジフェニルエーテル系(ビフェノ
ックス、クロメトキシニルなど)、ウレア系(ジウロン
、メチルダイムロン、DCMUなど)、アリールオキシ
プロピオン酸系(フルアジフォブなど)、カーバメート
系(IPCなど)の除草剤、
有機リン系(ECP剤、EPN剤、ESP剤、M E
P 剤など)、ピレスロイド系、塩素系(クロルデン、
ケルセン剤など)の殺虫剤の1種又は2種以上の混合物
が例示される。The present invention is characterized in that the hydrolysis and polycondensation reactions for forming the gel are carried out in the presence of an agricultural chemical component, or the gel is impregnated with the agricultural chemical component after gel formation. The agricultural chemical component that can be used here may be any component that is included in agricultural chemicals, as long as it is soluble in water or alcohol, or emulsifiable or dispersible with a surfactant. It is also possible to use agricultural chemicals that have been formulated into wettable powders, emulsions, liquids, aqueous solutions, and the like. Specifically, triazine series (simazine, atrazine, etc.), dinitroaniline series (triflualine, etc.), phenoxyacetic acid series (2,4-D, 2,4-PA, etc.), amide series (
butachlor, etc.), diphenyl ether-based (bifenox, chromethoxynil, etc.), urea-based (diuron, methyldaimeron, DCMU, etc.), aryloxypropionic acid-based (fluazifob, etc.), carbamate-based (IPC, etc.) herbicides, organophosphorus herbicides (ECP, etc.) agent, EPN agent, ESP agent, M E
P agents, etc.), pyrethroids, chlorine (chlordane,
Examples include one type of insecticide or a mixture of two or more types of insecticides such as Kelsen's agent.
これらの農薬成分は任意の量で用いることができるが、
通常ケイ酸エステルに対して0.1〜30重量%(以下
、%と略称する)、好ましくは1〜20%添加するのが
よく、農薬成分が水又はアルコール可溶の場合にはその
まま又は1〜50%濃度となるように水やアルコールに
溶解して加えるのがよく、溶解しない場合には、界面活
性剤等で水に乳化又は分散して添加するのがよい。尚、
農薬は酸性下で変質するものが多いので中性付近にpH
調整後添加するのが好ましい。These pesticide ingredients can be used in any amount, but
It is usually 0.1 to 30% by weight (hereinafter abbreviated as %), preferably 1 to 20%, based on the silicate ester, and if the agricultural chemical component is soluble in water or alcohol, it may be added as is or 1% by weight. It is preferable to add the compound by dissolving it in water or alcohol to a concentration of ~50%, or if it does not dissolve, it is preferable to emulsify or disperse it in water using a surfactant or the like and add it. still,
Many pesticides deteriorate under acidic conditions, so the pH should be around neutral.
It is preferable to add it after adjustment.
本発明においてアルキルシリケートの重縮合時に農薬成
分を存在させると、3次元化したSl−〇−3i結合に
農薬成分がからみあった状態でゲル化する。また、ゲル
化直後はSi −0−3i結合がゆるく、この状態のゲ
ルに農薬成分を含浸させても、ゲル奥深くまで農薬成分
が浸透し、反応中に農薬成分を添加した場合と同様の状
態となるのである。In the present invention, when an agrochemical component is present during polycondensation of alkyl silicate, the agrochemical component becomes gelled in a state in which it is entangled with the three-dimensional Sl-〇-3i bonds. In addition, immediately after gelation, the Si -0-3i bonds are loose, and even if the gel in this state is impregnated with pesticide ingredients, the pesticide ingredients will penetrate deep into the gel, resulting in the same state as when the pesticide ingredients are added during the reaction. It becomes.
上記ゲルの調整において、加水分解は低pHO方がはや
く、加水分解した液をゲル化させるのには、pHが高い
方がはやい。従って、効率的なゲル化は、低pH1例え
ばpH0,5〜3.0で加水分解後、中性付近、つまり
pH4,0〜8.0にpH調整するのがよい。In preparing the above-mentioned gel, hydrolysis is faster at lower pH, and gelation of the hydrolyzed liquid is faster at higher pH. Therefore, for efficient gelation, it is preferable to hydrolyze at a low pH 1, for example, pH 0.5 to 3.0, and then adjust the pH to around neutrality, that is, pH 4.0 to 8.0.
この際、液のpHを酸性にするには、塩酸、硝酸、硫酸
等の鉱酸及び酢酸、クエン酸、乳酸等の有機酸を用いる
のがよく、その後pHを中性付近に上昇させるには、ア
ンモニア水、水酸化ナトリウム、水酸化カリウム、モノ
エタノールアミン、ジェタノールアミン、トリエタノー
ルアミン、などを用いるのがよい。At this time, to make the pH of the liquid acidic, it is best to use mineral acids such as hydrochloric acid, nitric acid, and sulfuric acid, and organic acids such as acetic acid, citric acid, and lactic acid. , aqueous ammonia, sodium hydroxide, potassium hydroxide, monoethanolamine, jetanolamine, triethanolamine, etc. are preferably used.
又、反応系の水の量は、加水分解に必要な最低量あれば
よく、希釈されてゲル化しなくなるまで添加可能である
が、通常反応溶液中に0.5〜95%、好ましくは1〜
70%含有されるように用いるのがよい。尚、農薬成分
が親水性ならば水の量を多くするのが好ましい。In addition, the amount of water in the reaction system should be the minimum amount necessary for hydrolysis, and it can be added until it is diluted and no longer forms a gel, but it is usually 0.5 to 95%, preferably 1 to 95%, in the reaction solution.
It is preferable to use it so that the content is 70%. Note that if the agricultural chemical component is hydrophilic, it is preferable to increase the amount of water.
本発明では、上記ケイ酸エステルの加水分解によりアル
コールが生成するので、別にアルコールを添加する必要
はないが、アルコールはアノC中の農薬成分の分布を均
一にし、かつ農薬成分を可溶化するので、反応溶液中に
0.1〜95%含まれるようにするのがよい。尚、農薬
成分がアルコール可溶の場合は、アルコール量が多い方
が好ましい。In the present invention, since alcohol is generated by the hydrolysis of the silicate ester, there is no need to separately add alcohol, but alcohol makes the distribution of pesticide components in AnoC uniform and solubilizes the pesticide components. , preferably contained in the reaction solution in an amount of 0.1 to 95%. In addition, when the agricultural chemical component is alcohol-soluble, it is preferable that the amount of alcohol is large.
この際、別に添加するアルコールとしては、ケイ酸エス
テルの加水分解により生ずるアルコールと同種のものが
好ましいが、別の種類のものでもよい。At this time, the alcohol to be added separately is preferably of the same type as the alcohol produced by hydrolysis of the silicate ester, but a different type of alcohol may be used.
本発明では上記ゲル化反応を0〜80℃で行った後、農
薬成分を含有したゲルを常法により乾燥して乾燥ゲルを
製造し、これを粉砕して農薬を含有する粉体を得る。In the present invention, after the above-mentioned gelation reaction is carried out at 0 to 80° C., the gel containing the agricultural chemical component is dried by a conventional method to produce a dry gel, which is pulverized to obtain a powder containing the agricultural chemical.
この際ゲルの乾燥方法としては、ゲルを常圧又は減圧下
、0〜100℃、好ましくは15〜60℃でゲル重量が
変化しなくなるまで乾燥する。この乾燥工程で重縮合反
応はさらにすすみ、農薬成分をとじこめただままゲルは
しだいに堅くなる。At this time, the gel is dried under normal pressure or reduced pressure at 0 to 100°C, preferably 15 to 60°C, until the gel weight does not change. During this drying process, the polycondensation reaction progresses further, and the gel gradually becomes harder while still trapping the pesticide components.
次に、乾燥ゲルを粉砕するが、ゲルを粉砕したのち乾燥
してもよい。Next, the dried gel is ground, but the gel may be ground and then dried.
本発明においては、上記製造工程において、所望により
種々の成分を添加することができる。例えば得られる農
薬製剤の表面特性を変えるためにアルキルシリケート溶
液に^l ST is Z r等の金属アルコキシド、
ポリビニルアルコール、ポリビニルピロリドン、ポリエ
チレングリコール、ポリアクリルアミド、ポリアクリル
酸、ポリアクリル酸エステノペポリ酢酸ビニル、グアー
ガム、カラギーナン、ヒドロキシエチルセルロース、ヒ
ドロキシプロピルセルロースなどの高分子や農薬担体用
無機粉体を添加することができる。In the present invention, various components can be added as desired in the above manufacturing process. For example, metal alkoxides, such as
Polymers such as polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, polyacrylamide, polyacrylic acid, polyacrylate esternope, polyvinyl acetate, guar gum, carrageenan, hydroxyethylcellulose, hydroxypropylcellulose, and inorganic powders for agricultural chemical carriers can be added. .
本発明によれば、雨に強く持続性のある農薬製剤が得ら
れる。従って、これによれば農薬の過剰な拡散を防止し
、薬害を防止することができる。According to the present invention, a pesticide formulation that is resistant to rain and has a long-lasting effect can be obtained. Therefore, according to this, excessive diffusion of agricultural chemicals can be prevented and chemical damage can be prevented.
又、農薬成分として除草剤を選ぶと、本発明の除草剤は
非選択性であっても選択性を与える製剤となり、土表面
のみの雑草に作用し、土中への拡散が小さいため、作物
に害を与えないというすぐれた効果が発揮される。In addition, when a herbicide is selected as the agricultural chemical component, the herbicide of the present invention becomes a formulation that provides selectivity even if it is non-selective, and acts only on weeds on the soil surface, and its diffusion into the soil is small, so it is effective against crops. It has an excellent effect of not causing any harm to the people.
従って農薬成分として、除草剤、殺虫剤、殺菌剤、殺そ
剤及び植物生長促進剤などを選択することにより広範囲
の農薬として使用できる。Therefore, it can be used as a wide range of agricultural chemicals by selecting herbicides, insecticides, fungicides, rodenticides, plant growth promoters, etc. as agricultural chemical components.
次に実施例により本発明を説明するが本発明はこれらに
限定されるものではない。Next, the present invention will be explained with reference to Examples, but the present invention is not limited thereto.
実施例1
si(OC28s)、 52.1 g (0,25モル
)に28mmo 1 / 12の塩酸水22.5 gを
加え撹拌して1時間後に均一溶液を得た。この液にメチ
ルダイムロン1.25g。Example 1 22.5 g of 28 mmol 1/12 hydrochloric acid water was added to 52.1 g (0.25 mol) of si(OC28s) and stirred to obtain a homogeneous solution after 1 hour. Add 1.25 g of Methyl Daimeron to this liquid.
DcMUl、5g、2.4−PA、0.75gを添加し
て撹拌したところ15分後にゲル化した。このゲルを4
5℃で1週間乾燥後、粉砕して除草剤を含むシリカ粉体
を得た。When 5 g of DcMUl and 0.75 g of 2.4-PA were added and stirred, gelation occurred after 15 minutes. 4 times this gel
After drying at 5° C. for one week, it was crushed to obtain silica powder containing the herbicide.
この除草製剤の耐水性及び徐放性を調べるために、本発
明製剤1.5gを2Qmj!の水で水洗し、その濾液を
とり、再度水洗をくり返した。各濾液を脱脂綿にしみこ
ませ、その上にメヒシバの種子20コをうえ、1週間後
の発芽率を調べた。In order to examine the water resistance and sustained release properties of this herbicidal preparation, 1.5 g of the preparation of the present invention was mixed with 2Qmj! The filtrate was collected and the washing was repeated again. Absorbent cotton was soaked with each filtrate, 20 crabgrass seeds were placed on top, and the germination rate was examined one week later.
比較として同量の除草剤を湿式法シリカに吸着させたも
のを用いた。For comparison, the same amount of herbicide was adsorbed onto wet silica.
水洗回数とその濾液中のメヒシバの発芽率を表−1に示
す。Table 1 shows the number of times of water washing and the germination rate of crabgrass in the filtrate.
表−1
」
[
表−1より水洗1回目の濾液中では本発明品、比較品と
もにメヒシバの発芽はみられず、ともに水中に除草剤が
放出されていることがわかる。しかし、水洗2回目の濾
液中では本発明品では発芽はみられないのに対し、比較
例では50%のメヒシバが発芽し、除草効果が失なわれ
ていることがわかる。これは1回目の水洗で比較例のシ
リカに吸着していた多量の除草剤が水中に放出されてし
まったためと考えられる。これに対して、本発明品では
5回の水洗においても20%の発芽率で除草効果を示し
ており、このような過酷な条件下においても徐放性、持
続性ともに優れていた。Table 1 [From Table 1, it can be seen that no germination of crabgrass was observed in the filtrate of the first washing with water in both the inventive product and the comparative product, indicating that the herbicide was released into the water in both cases. However, in the filtrate of the second washing with water, no germination was observed in the product of the present invention, whereas in the comparative example, 50% of the crabgrass germinated, indicating that the herbicidal effect was lost. This is thought to be because a large amount of the herbicide adsorbed on the silica of the comparative example was released into the water during the first water washing. On the other hand, the product of the present invention showed a herbicidal effect with a germination rate of 20% even after 5 washings, and was excellent in both sustained release and sustainability even under such harsh conditions.
実施例2
エチルシリケート40 37.5gに28mmo 1
/ 1の塩酸水22.5 gを加え撹拌して1時間後に
均一溶液を得た。この液を172規定のアンモニア水で
pH5に調整したのち、ラッソー乳剤5gを添加して撹
拌した。この液を45℃で1夜間放匿してゲル化させた
。このゲルを減圧乾燥後粉砕して除草剤を含むシリカ粉
体を得た。トウモロコシの種子を地表面下3cmのとこ
ろに植え、種子を植えた地点から5 cm離れた円周上
にこの粉体を散布した。Example 2 Ethyl silicate 40 28 mmo 1 in 37.5 g
22.5 g of 1/1 hydrochloric acid solution was added and stirred to obtain a homogeneous solution after 1 hour. After adjusting the pH of this liquid to 5 with 172N aqueous ammonia, 5 g of lasso emulsion was added and stirred. This solution was allowed to stand overnight at 45°C to form a gel. This gel was dried under reduced pressure and then ground to obtain silica powder containing the herbicide. Corn seeds were planted 3 cm below the ground surface, and the powder was spread on a circumference 5 cm away from the point where the seeds were planted.
その後、その粉体上に3日間にわたり各日1回づつジヨ
ウ口で水をまいたのち、メヒシバの種子を粉体上にまい
た。又、比較として湿式法で合成したシリカに同量のラ
ッソー乳剤を吸着させたものを用いて上記操作を行った
。Thereafter, the powder was sprinkled with water once each day for three days, and then the seeds of crabgrass were sown on the powder. In addition, as a comparison, the above operation was carried out using silica synthesized by a wet method to which the same amount of lasso emulsion was adsorbed.
本発明品の場合、メヒシバは発芽しなかったのに対して
、トウモロコシは正常に発芽した。一方、比較例の場合
、メヒシバは30%の発芽率を示したのに対し、トウモ
ロコシは発芽せず薬害があられれた。In the case of the product of the present invention, crabgrass did not germinate, whereas corn germinated normally. On the other hand, in the case of the comparative example, crabgrass showed a germination rate of 30%, whereas corn did not germinate and suffered from chemical damage.
Claims (2)
〕 (式中、R_1〜R_4は、水素又は C_xH_2_k_+_1(OC_2H_4)_y−(
但し、xは1〜5、yは0〜10の整数を示す。)で示
される基であるが、R_1〜R_4のすべてが水素であ
ることはない。nは0〜20の整数である。) で表わされる少なくとも1種のアルキルシリケートの加
水分解、重縮合反応を農薬成分の存在で行ってゲルを形
成させた後、又は該反応によりゲルを形成した後に農薬
成分を該ゲルに含浸させた後、乾燥することを特徴とす
る農薬製剤の製造方法。(1) General formula [I]: ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・[I
] (In the formula, R_1 to R_4 are hydrogen or C_xH_2_k_+_1(OC_2H_4)_y-(
However, x represents an integer of 1 to 5, and y represents an integer of 0 to 10. ), but not all of R_1 to R_4 are hydrogen. n is an integer from 0 to 20. ) A hydrolysis or polycondensation reaction of at least one alkyl silicate represented by the following formula is performed in the presence of a pesticide component to form a gel, or after a gel is formed by the reaction, the gel is impregnated with a pesticide component. A method for producing an agrochemical formulation, which comprises drying the formulation.
項記載の方法。(2) Claim No. (1) in which the agricultural chemical component is a herbicide
The method described in section.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5760387A JPS63225301A (en) | 1987-03-12 | 1987-03-12 | Production of agricultural chemical pharmaceutical |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5760387A JPS63225301A (en) | 1987-03-12 | 1987-03-12 | Production of agricultural chemical pharmaceutical |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS63225301A true JPS63225301A (en) | 1988-09-20 |
Family
ID=13060432
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP5760387A Pending JPS63225301A (en) | 1987-03-12 | 1987-03-12 | Production of agricultural chemical pharmaceutical |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS63225301A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11263702A (en) * | 1997-12-11 | 1999-09-28 | Rohm & Haas Co | Sustained-release composition |
JP2006199630A (en) * | 2005-01-21 | 2006-08-03 | Nippon Soda Co Ltd | Sustained-release agricultural chemical composition and its production method |
JP2010053056A (en) * | 2008-08-27 | 2010-03-11 | Tokyo Metropolitan Industrial Technology Research Institute | Sustained release preparation and method for producing the same |
-
1987
- 1987-03-12 JP JP5760387A patent/JPS63225301A/en active Pending
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11263702A (en) * | 1997-12-11 | 1999-09-28 | Rohm & Haas Co | Sustained-release composition |
JP2006199630A (en) * | 2005-01-21 | 2006-08-03 | Nippon Soda Co Ltd | Sustained-release agricultural chemical composition and its production method |
JP2010053056A (en) * | 2008-08-27 | 2010-03-11 | Tokyo Metropolitan Industrial Technology Research Institute | Sustained release preparation and method for producing the same |
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